低值稳定的铜纳米合金光催化剂的制备及其催化氢胺化反应的研究

氢胺化反应是制备高附加值的含氮的医药化合物的重要方法，需要在催化剂存在下才能进行。现有催化剂主要是过渡金属配合物，需要较高温度活化反应分子，但高温限制了其转化率。此外，配合物还存在着成本昂贵、反应后分离困难等问题。因而开发低值高效、低温下工作的多相催化剂势在必行。本项目提出以廉价的铜合金纳米颗粒为光催化剂，利用其在可见光照射下的局域表面等离子体共振（LSPR）吸收产生高能电子，从而直接进攻并活化吸附在金属表面的反应分子，降低反应的活化能，实现低温下高效催化氢胺化反应。项目将采用铜与具有较小功函数的金属形成合金的方法，使铜活性位注入更多的电子参与反应，通过选择合金元素以及调整合金组分实现双重作用，同时解决铜纳米合金的化学和热稳定性以及金属电子能级与氢胺化反应物的LUMO轨道能级匹配等关键科学问题。本项目的实现对功能金属合金的应用开发以及含C-N键化合物的绿色催化合成都具有重要意义。

Hydroamination reaction is a significant method in the fabrication of valuable N-containing chemicals. The current catalysts are metal coordination complexes, which are expensive and difficult to separate after reaction. It is still a challenge to achieve high conversion using low-value heterogeneous catalyst. Based on our preliminary study, we proposed a novel design to prepare chemical and thermal stable plasmoinc copper alloy nanoparticles, which will be used for photocatalytic hydroamination reaction under visible light illumination at low temperatures. Copper alloy nanoparticles can significantly absorb visible light due to the localized surface plasmon (LSPR) effect and generate high energy electrons. The electrons can activate molecules absorbed on the surface of metals, initiate reaction and reduce the reaction activation energy. In this project, we will prepare copper alloys using metals with smaller work function and adjust the alloy composition and content in order to solve two key scientific problems: obtaining stable Cu alloy and tuning the electron structure to match the LUMO orbital of reactant. We will investigate the influence of catalyst structure and catalytic parameters on the catalytic hydroamination reaction, screen high active structure and reaction condition, and uncover the catalytic mechanism. The project has the scientific significance for the development of functional alloys and for the synthesis of N-containing chemicals in a green manner.